CA2214363C - Method of producing synthetic silicates and use thereof in glass production - Google Patents
Method of producing synthetic silicates and use thereof in glass production Download PDFInfo
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- CA2214363C CA2214363C CA002214363A CA2214363A CA2214363C CA 2214363 C CA2214363 C CA 2214363C CA 002214363 A CA002214363 A CA 002214363A CA 2214363 A CA2214363 A CA 2214363A CA 2214363 C CA2214363 C CA 2214363C
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
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- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Glass Compositions (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
A method is disclosed of producing a calcium silicate precursor material.
The method is advantageous in providing material useful in glass making. Such method involves the reaction of calcium oxides and magnesium oxides, water and sodium silicates. The glass formation is performed at a lower temperature than usual and performed with a lower amount of volatile gas release. Less cristobalite formation in the glass occurs.
The method is advantageous in providing material useful in glass making. Such method involves the reaction of calcium oxides and magnesium oxides, water and sodium silicates. The glass formation is performed at a lower temperature than usual and performed with a lower amount of volatile gas release. Less cristobalite formation in the glass occurs.
Description
_1_ ,~V1ETFIOD OF PRODUCING SYNTHETIC SIL,ICA.TES
,AND 'llSF TIiEREOF IN GLASS PRODL1GTION
F1EL,D 4F INVENTION
The present invention relates to glass making compositions and methods.
More particularly, the present invention relates to a calcium silicate precursor material made fiom calcium oxides and magnesium oxides, Water and soditcm silicates.
Such material is particularly useful in Glass making and affords using lower texrtperatures with less volatiles than previously.
EACKGROUND OF THE INVEN°flON
Glass can be produced from Glass Furmers, which can be theorised under the random-network theory of glass as material having heavy canon - oxygen bond strengths greater than about 335 kilo Joules per mole. Typical formers are oxides such as Bz43, .SiOz, GeOz, Pz4s, AszOs, P~U3, AszO~, SbzO~, V,Os, Sb2Us, Nb2Us, and T'a20s.
The fluoride BeF2 also qualifies. Additional components can be mixed with glass formcrs to provide various effects. These components include glass intermediates, having, bond strengths of about 250-350 kilo-Joules/mole, and which may or may not become part of the network; and glass modifiers, having bond strengths of less than about 250 kilo Joules per mole, a~ad which do not become part of the network.
Typical modifiers are oxides of gallium, magnesium, lithium, Zinc, ealeiunn, sodiutzt and potassium. Other formcrs, intermediates and modifiers arc lcnown; as illustrated in "GLASS", Kirk-Othmer Ene~olopr is of Cherrtical TechtaoloQV '101. I z, pp 555 +
(1994).
Onc form of glass is a silicate system containing modifiers and intermediates. Such silicates have a network of siliam to oxygen to silicon bonds.
Use of a modifier, such as sodium oxide, can cleave these bonds by forming a silicon to oxygen to terminal sodium linkage. Other modifiers cao be used. Such modifiers can make the glass more fluid, decrease resistivity, increase thermal expansion, lower chemical durability or increase flux.
Such sodium silicates have uses for adhesives, cleaners, desiccants, abrasives, cement deflocculants, and surface coatings.
The predc~minaie glass produced is soda-lime glass. Such soda-lime glasses cant involve mixtures of alkali and alkali earths. These; glasses can be
,AND 'llSF TIiEREOF IN GLASS PRODL1GTION
F1EL,D 4F INVENTION
The present invention relates to glass making compositions and methods.
More particularly, the present invention relates to a calcium silicate precursor material made fiom calcium oxides and magnesium oxides, Water and soditcm silicates.
Such material is particularly useful in Glass making and affords using lower texrtperatures with less volatiles than previously.
EACKGROUND OF THE INVEN°flON
Glass can be produced from Glass Furmers, which can be theorised under the random-network theory of glass as material having heavy canon - oxygen bond strengths greater than about 335 kilo Joules per mole. Typical formers are oxides such as Bz43, .SiOz, GeOz, Pz4s, AszOs, P~U3, AszO~, SbzO~, V,Os, Sb2Us, Nb2Us, and T'a20s.
The fluoride BeF2 also qualifies. Additional components can be mixed with glass formcrs to provide various effects. These components include glass intermediates, having, bond strengths of about 250-350 kilo-Joules/mole, and which may or may not become part of the network; and glass modifiers, having bond strengths of less than about 250 kilo Joules per mole, a~ad which do not become part of the network.
Typical modifiers are oxides of gallium, magnesium, lithium, Zinc, ealeiunn, sodiutzt and potassium. Other formcrs, intermediates and modifiers arc lcnown; as illustrated in "GLASS", Kirk-Othmer Ene~olopr is of Cherrtical TechtaoloQV '101. I z, pp 555 +
(1994).
Onc form of glass is a silicate system containing modifiers and intermediates. Such silicates have a network of siliam to oxygen to silicon bonds.
Use of a modifier, such as sodium oxide, can cleave these bonds by forming a silicon to oxygen to terminal sodium linkage. Other modifiers cao be used. Such modifiers can make the glass more fluid, decrease resistivity, increase thermal expansion, lower chemical durability or increase flux.
Such sodium silicates have uses for adhesives, cleaners, desiccants, abrasives, cement deflocculants, and surface coatings.
The predc~minaie glass produced is soda-lime glass. Such soda-lime glasses cant involve mixtures of alkali and alkali earths. These; glasses can be
-2-produced using oxides ol'svdium, calcium, silicon, ln,agnesium, aluminum, barium and potassium.
Most glass is manufactured by a pzocess in which craw materials are converted at laigh temperatures to a homogeneous melt that is then formed. The raw znatcrials used are typically sand, its the source of silicon; limestone, as the source of calcium and magnesium; and soda ash or caustic soda, as the s()urCe of sodium.
Tlte limestone is typically a high calcium limestone (95% calcite, CaCU3), aragoautc mineral, or a dolomitic limestone (mixucre of dolomite, CaM.g(CO~).,, and calcite). 'fhc soda ash (sodium carbonate, Na2CU~) can be a Solway process product or mineral deposit. Typical manufacturing processes involve the batch mixing of sand, soda ash, limestone a~~d other materials at elevated telnperatures above 1000°C.
There is a continued need for new processes and materials which.
facilitate the production of glass and which provide enezgy and materi~rl savings.
BELATED ART
U.S. Patent No. 5,004,706 discloses a method of molten glass wherein silica is heated with a batch eomp4nent comprising a sodium alkaline earth silicate which includes a major portion of the soditun in the restlltanl molten glass.
The patent also discloses a batch cvxnponent for use in glass manufacture, cox~prising sodium calcium silicate, and, optionally, sodium magnesium silicate. A method for producing a batch component comprising sodium calcium silicate is also disclosed, eomprisizte heating a mixture of a svuzce of sodium oxide, a source of silica, and eitlter a source of calcium silicate or a source of calcium oxide at a temperatuze of greater than about 80Q°C., with a NazO, CaQ, and SiQ2 molar ratio of 1:1:1. The resulting batch components can be preheated without melting prioz to mixing and feeding the furnace.
U.S. Patent No. 4,920,080 discloses a method of mahinb glass in which ,silica is raacted with sodium carbonate io form sodium silicate: :~ a preliminary step.
The resulting radium silicate is combined with a calcium carbonate -containing batch material which has been preferably ealeined to release carbon dioxide prior, to contacting with the sodium silicate. The patent suggests that the process maximizes the 3U recovery of waste heat from glass melting and that the resulting batch materials are substantially lTec of carbon dioxide which minimizes gaseous inclusions in tlae glass.
U.S. Patent No. 4,023,976 diselosev an improved process for making
Most glass is manufactured by a pzocess in which craw materials are converted at laigh temperatures to a homogeneous melt that is then formed. The raw znatcrials used are typically sand, its the source of silicon; limestone, as the source of calcium and magnesium; and soda ash or caustic soda, as the s()urCe of sodium.
Tlte limestone is typically a high calcium limestone (95% calcite, CaCU3), aragoautc mineral, or a dolomitic limestone (mixucre of dolomite, CaM.g(CO~).,, and calcite). 'fhc soda ash (sodium carbonate, Na2CU~) can be a Solway process product or mineral deposit. Typical manufacturing processes involve the batch mixing of sand, soda ash, limestone a~~d other materials at elevated telnperatures above 1000°C.
There is a continued need for new processes and materials which.
facilitate the production of glass and which provide enezgy and materi~rl savings.
BELATED ART
U.S. Patent No. 5,004,706 discloses a method of molten glass wherein silica is heated with a batch eomp4nent comprising a sodium alkaline earth silicate which includes a major portion of the soditun in the restlltanl molten glass.
The patent also discloses a batch cvxnponent for use in glass manufacture, cox~prising sodium calcium silicate, and, optionally, sodium magnesium silicate. A method for producing a batch component comprising sodium calcium silicate is also disclosed, eomprisizte heating a mixture of a svuzce of sodium oxide, a source of silica, and eitlter a source of calcium silicate or a source of calcium oxide at a temperatuze of greater than about 80Q°C., with a NazO, CaQ, and SiQ2 molar ratio of 1:1:1. The resulting batch components can be preheated without melting prioz to mixing and feeding the furnace.
U.S. Patent No. 4,920,080 discloses a method of mahinb glass in which ,silica is raacted with sodium carbonate io form sodium silicate: :~ a preliminary step.
The resulting radium silicate is combined with a calcium carbonate -containing batch material which has been preferably ealeined to release carbon dioxide prior, to contacting with the sodium silicate. The patent suggests that the process maximizes the 3U recovery of waste heat from glass melting and that the resulting batch materials are substantially lTec of carbon dioxide which minimizes gaseous inclusions in tlae glass.
U.S. Patent No. 4,023,976 diselosev an improved process for making
-3-glass in which a glass batch is mixed with a binder, aged, compacted, and compressed into briquettes, which are heated to partially read the ccmtents of tlae batch in a prcrcaction stage. This process minimizes segregation and non-uni fom~iiy its the Mass batch, and reduces the operating temperature of the glass furnace.
U.S. latent No. :1,883,364 discloses a dust-free granular alkaline earth carbonate material particularly soiled l~~r feed stock for glass furnaces.
'fhe process for preparing the granular material involves combining a freshly prepared aqueous slurry of alkaline earth carbonate with a wlution of alkali silicate, drying the slurry and sintering at temperatures of about 7UU-9U0°C., thereby conwertino the aqueous slurry solids to a dense material which can be ground to a dust-free, free flowing form suitable ~or use as a Iced stock in glass furnaces.
U.S_ Patent No. 3,967,943 discloses a method of improving glass batch melting by using sodium silicate water solution as a batch ingredient to supply from about l% tee about 10% of the total NalO content, with conventional sodium-cantainiug batch nr~aterials supplying the bulk of the NayU eontoni. The Patent suggests that the addition of sodiwn silicate water solutiem enables a lower tcmperaturer andlor less fuel to be used in melting, ~~esults in lower dusiirtl;, and reduces the incidence of' glass inhomogeneities oz defects.
SUMMARY
2U The present invention provides a method of producing a calcium silicate precursor material. The method is advantageous in providing material useful in glass making from the reaction of calcium oxides and magnesium oxides, water and sodium silicates. The l;lass formation is perfonncd at a lower temperature than usual and performed with a lower amount of volatile gas release. Less cristobaliie formation in the glass occurs. The zr~ethod embodies the step of admixing a slaked source of calcium and a soluble silicate to produce a calciwn silicate precursor material. This precursor material optionally ccmtaitas free water, which can be residual fiom. the slaking process for pre~ducing the slaked source of calcium. Th.e method further comprises mixing the calcium silicate precursor material and a source of silica to 30 produce a glass product.
~N1J30b1MENTS Oh THE PRFSEN1' 1NVENT10N
Ono embodiment of the present invention is a method of producing a
U.S. latent No. :1,883,364 discloses a dust-free granular alkaline earth carbonate material particularly soiled l~~r feed stock for glass furnaces.
'fhe process for preparing the granular material involves combining a freshly prepared aqueous slurry of alkaline earth carbonate with a wlution of alkali silicate, drying the slurry and sintering at temperatures of about 7UU-9U0°C., thereby conwertino the aqueous slurry solids to a dense material which can be ground to a dust-free, free flowing form suitable ~or use as a Iced stock in glass furnaces.
U.S_ Patent No. 3,967,943 discloses a method of improving glass batch melting by using sodium silicate water solution as a batch ingredient to supply from about l% tee about 10% of the total NalO content, with conventional sodium-cantainiug batch nr~aterials supplying the bulk of the NayU eontoni. The Patent suggests that the addition of sodiwn silicate water solutiem enables a lower tcmperaturer andlor less fuel to be used in melting, ~~esults in lower dusiirtl;, and reduces the incidence of' glass inhomogeneities oz defects.
SUMMARY
2U The present invention provides a method of producing a calcium silicate precursor material. The method is advantageous in providing material useful in glass making from the reaction of calcium oxides and magnesium oxides, water and sodium silicates. The l;lass formation is perfonncd at a lower temperature than usual and performed with a lower amount of volatile gas release. Less cristobaliie formation in the glass occurs. The zr~ethod embodies the step of admixing a slaked source of calcium and a soluble silicate to produce a calciwn silicate precursor material. This precursor material optionally ccmtaitas free water, which can be residual fiom. the slaking process for pre~ducing the slaked source of calcium. Th.e method further comprises mixing the calcium silicate precursor material and a source of silica to 30 produce a glass product.
~N1J30b1MENTS Oh THE PRFSEN1' 1NVENT10N
Ono embodiment of the present invention is a method of producing a
-4-molten glass comprising the step of admixing a slaked source of calcium and a soluble silicate to produce a calciwn silicate precursor material. This precursor material optionally contains free water, which can be residual I:rom vhe slaki~n8 process for producing the slaked source of calcium. The method further comprises nxixuig the ectlcium silicate precursor material and a source of silica to produce a glass product.
The source of calcium ctln be any type of a natural or synthesi~..c;d material capable of being slaked by water; that is, an oxide of calcium which reacts with water. Such sources may be natural forms of oxides of calcium or processed materials which has been 6rouad, calcined or otherwise treated. Non-limiting examples are wollastonite (CaU~SiOz), diopside (Ca0~MgU~2SiU2), akermanite (2Ca0~Mg0~2SiOZ), calcium metasilieat~ (CaU~SiOz), calcincd dolomite (i.e., dolomitic lime, Ca0~Mg0), and lime (Ca0) in. its various forms, e.g., quicklime, hydrated litn~e, hydraulic lime and high calcium lime (i.e., 95% or more active).
A preferred selection of source of calcium is dolomitic lime and high calcium lime. 1"hc calcium source can be slaked with water at ambient temperatures or pressures. Higher temperatures and pressures can be used. When more than one type of calcium source is used, the calcium sources may be mixed before, during or after slaking. 'fhc amount of water used preferably is at least a stoichmelric amount for complete slaking and can be an amount Uf water in excess such that the slaked Source ZO of calcium comprises an amount of free (unrcacted) watcr_ Tlte soluble silicate is a silicate having sufficient solubility in water to enable the silicate to react with the slaked source of calcium.
A preferred soluble silicate is a scodium silicate. Such sodium silicate can be dry or liquid and anhydrous or hydrated, preferably pentahydrated.
In addition to the source of silica, there zr~ay also be receded one or more c~f a source of calcium, m~n;esium and sodium io compl.ete the production of glass.
laor instance, one or more of limes-lone, dolomite and soda ash materials might be used.
This depends upon the desired glass composition. The use o~ such materials can result in the release of volatile gases, such as carbonates, in the glass production and, 30 accordingly, use ~I' such is desired to be minimal.
In one preferred embodiment, the sodium silicate is an anhydrous or hydrated form of a compound havint; the empirical Fc~nnula of NaZU~ X Sin,, wherein
The source of calcium ctln be any type of a natural or synthesi~..c;d material capable of being slaked by water; that is, an oxide of calcium which reacts with water. Such sources may be natural forms of oxides of calcium or processed materials which has been 6rouad, calcined or otherwise treated. Non-limiting examples are wollastonite (CaU~SiOz), diopside (Ca0~MgU~2SiU2), akermanite (2Ca0~Mg0~2SiOZ), calcium metasilieat~ (CaU~SiOz), calcincd dolomite (i.e., dolomitic lime, Ca0~Mg0), and lime (Ca0) in. its various forms, e.g., quicklime, hydrated litn~e, hydraulic lime and high calcium lime (i.e., 95% or more active).
A preferred selection of source of calcium is dolomitic lime and high calcium lime. 1"hc calcium source can be slaked with water at ambient temperatures or pressures. Higher temperatures and pressures can be used. When more than one type of calcium source is used, the calcium sources may be mixed before, during or after slaking. 'fhc amount of water used preferably is at least a stoichmelric amount for complete slaking and can be an amount Uf water in excess such that the slaked Source ZO of calcium comprises an amount of free (unrcacted) watcr_ Tlte soluble silicate is a silicate having sufficient solubility in water to enable the silicate to react with the slaked source of calcium.
A preferred soluble silicate is a scodium silicate. Such sodium silicate can be dry or liquid and anhydrous or hydrated, preferably pentahydrated.
In addition to the source of silica, there zr~ay also be receded one or more c~f a source of calcium, m~n;esium and sodium io compl.ete the production of glass.
laor instance, one or more of limes-lone, dolomite and soda ash materials might be used.
This depends upon the desired glass composition. The use o~ such materials can result in the release of volatile gases, such as carbonates, in the glass production and, 30 accordingly, use ~I' such is desired to be minimal.
In one preferred embodiment, the sodium silicate is an anhydrous or hydrated form of a compound havint; the empirical Fc~nnula of NaZU~ X Sin,, wherein
-5-X ranges in value from. 0.5 to 3.75; preferably, NazO~Si~z, Na20~Sinz~SHZO and NaiO~10/3SiOz. When the sodium silicate is anhydrous, tlac sodiunn silicate is preferably admixed with the slaked source of calcium after completion of the slaking process.
The admixing of the slaked source of calcium and the soluble silicate can be rerformed simultaneously with or altez the slaking to produce the slaked source.
The proportion of the source of calcium, water for slaking and soluble silicate can be Varied to produce a variety of calcium silicate precursor material. In a preferred embodiment the source of calcitun is a bland of dolomiric lime and high calcium lime.
1 U 'fhc proportion of the blend can Vary, preferably the weight ratio of dolomitic lime to high calcium time ranges from about 100:1 to about 1:100, more preferably from about 4:1 to about 2:1. The preferred weight ratio of water to lime during slaking is about x0:1 to about 0.35:1, more preferably about 2.S:I to about I:1. 'fhe water temperature for the slaking of the calcium source is pzeferably fzonn about 10°C.
to about 90°C., more preferably about 20°C. to about 30°C.
The admixing of the water and the source of calcium can be in either order of one to the other or concurrent. Preferably the water is added to the source of calcium over a pericyd of time, such as from about S Seconds to about 2 houzs, preferably about 30 seconds. The slaking time is preferably from about 1 minute to 20 about 60 minutes, more preferably about 2.5 minutes to about 10 minutes.
The azno~mt of the soluble silicate to be admixed with tkre slaked source c~f calciuzrt preferably ranges in the weight ratio of soluble silicate to slaked source of calcium (dry) of hom about 0.044 to about 2.2, more prcfErably about 0:048 to about 1.2. The time ol' admixing of the soluble silicate and the staked source of calcium can preferably range from about 5 seconds to about 2 hours, more preferably about seconds to about 30 seconds. Tl~e admixture of soluble silicate and slaked source of calcium is preferably treacrd to continued mixing of from about 5 minutes to about 2 hours, more preferably about 3U minutes to about 1 laour_ The admixing and continued mixing, if any, of the soluble silicate and 30 the slaked source of calcium i.s effeetiVe to produce a calcium silicate precursor material suitable for the production of glass. When a excess of water (e.g.
free wafer) is present, the material is in a slurry fvrzn. Depending upon the composition and type
The admixing of the slaked source of calcium and the soluble silicate can be rerformed simultaneously with or altez the slaking to produce the slaked source.
The proportion of the source of calcium, water for slaking and soluble silicate can be Varied to produce a variety of calcium silicate precursor material. In a preferred embodiment the source of calcitun is a bland of dolomiric lime and high calcium lime.
1 U 'fhc proportion of the blend can Vary, preferably the weight ratio of dolomitic lime to high calcium time ranges from about 100:1 to about 1:100, more preferably from about 4:1 to about 2:1. The preferred weight ratio of water to lime during slaking is about x0:1 to about 0.35:1, more preferably about 2.S:I to about I:1. 'fhe water temperature for the slaking of the calcium source is pzeferably fzonn about 10°C.
to about 90°C., more preferably about 20°C. to about 30°C.
The admixing of the water and the source of calcium can be in either order of one to the other or concurrent. Preferably the water is added to the source of calcium over a pericyd of time, such as from about S Seconds to about 2 houzs, preferably about 30 seconds. The slaking time is preferably from about 1 minute to 20 about 60 minutes, more preferably about 2.5 minutes to about 10 minutes.
The azno~mt of the soluble silicate to be admixed with tkre slaked source c~f calciuzrt preferably ranges in the weight ratio of soluble silicate to slaked source of calcium (dry) of hom about 0.044 to about 2.2, more prcfErably about 0:048 to about 1.2. The time ol' admixing of the soluble silicate and the staked source of calcium can preferably range from about 5 seconds to about 2 hours, more preferably about seconds to about 30 seconds. Tl~e admixture of soluble silicate and slaked source of calcium is preferably treacrd to continued mixing of from about 5 minutes to about 2 hours, more preferably about 3U minutes to about 1 laour_ The admixing and continued mixing, if any, of the soluble silicate and 30 the slaked source of calcium i.s effeetiVe to produce a calcium silicate precursor material suitable for the production of glass. When a excess of water (e.g.
free wafer) is present, the material is in a slurry fvrzn. Depending upon the composition and type
-6-of glass to be formed using the calcium silicate precursor material, additional material can be added to the slurry during or after admixing or mixing. For instance, if additional silica is desired, a silica sowce, such as silica flour, can be added. Also, before such calcium silicate precursor z~~atarial is med in glass production, the slurry can be treated, such as by filtering, evaporating of heating, to zernove at least a portion of the free water. For instance, the slurry could be dried at a tem.peraiure of about 110°C.
'fhe calcium sylieatc precursor material c;an be further tzeated by heating at higher, temperatures, such as from about 110°C. to about 1100°C., mura preferably lU from about 150°C. to about 700°C., even more preferably below about 300°C. The time and tamping of such healing can be varied, depending upon the desired final calcium silicate precuru~r material inasmuch as such heating can produce fuuhez oz continued reactions.
The calcium silicate precursor material produced by the present invention can have a wide variety of one or more calcium silicate components. 'fhe Variability of calcium silicate components correlates with the variability of amounts of the source of calcium, water and tlae soluble silicate, as well as the conditions of operating, e.g., temperatures, pressures, lime, mixing, ere. 'fhe preferzed calcium silicate components have the formula NaACaB(U)~~UH)"Si~,O~:~G1v20 whezein either C or 1J is zero and the 20 othez subscripted letters vary according to conditions a.~ previously described. Table T
discloses, in a non-limiting way, the pos57ble correlations attainable between operating amounts and calcium silicate precursor material attainable.
Weight Ratios Lime ~ Water ~ Soluble Silica ~ Product 1 1 I 0.5 Cas(OH)ZSibO,~4I~h0 1 1 0.7 C'.aS(OIr)~Si~O,~4H2U
1 3.3 1.7 Ca.,(UI~)ZSi~0,64H.,0 :
1 3.3 0.7 (Ca0),.sSiUiH,O
1 3.3 1.2 (Ca0),,5Si().,HZO
1 7 1.1 Ca0Si02 )<1z0 in a preferred embodiment, the calcium silicate precursor material coanprises one or more components represented by the formula (Ca0)~~SiOZ~Y
(HZO), wherein x is from 5/6 to 3/2 and Y is no zero. Mnre preferably ~c is I .5 and Y is 1.
In another preferred embodiment, the calcium silicate precursor material comprises one or more components represented by the formula X(NazO)~Y(CaU)~Si02 and optionally comprises a compouxad represented by the formula W(NazO)~V(Mp0)~SiO.,, wherein X and W independently arc from l/G to 1/1 and W
and V independently are from 113 to 1/l. Preferably, the; calcium silicate precursor material comprises 0.5(NaZU)~1(Ca0)~Si02. More preferably, the calcium silicate precursor material further comprises Naz,O~Mgt)~SiO,.
In another aspect, the present invention is the setting of process variables within a set of novel process ~ariabtes to attain desired results.
Accordingly, the present ia~,venticm can be the above-described invention wherein the proportion of the amount of calcium silicate precursor material and the amount oJf' tlxe source of silica is effccti~cly controlled to reduce the temperature required to pruduce the molten glass within a set time. l~lternatively, tlae propurtiun eU' the amount of calciuat~
silicate precursor rn.atezial and the amount of the source of silica is effectively controlled to reduce the time required to produce the moltcr~ glass at a set temperature.
'~'be _g_ variables which compose the foregoing variables can also be controlled. 1~or instance, the molten glasa is produced by setting variables from the set of variables consisfiing of the ~atn,ount of slaked Source of calcium,, the amount of soluble silicate, the amount of free water, the amount of the source of silica, tlae time to produce the molten glass, and the temperature to produce the molten glass. Once a certain number of the variables hare been set, the remaining are fixed in accordance with the degree of freedom.
Depending upon the glass composition desired, the amounts cal' other sources of calcium, magnesiutm yr sodium, such as limestone, dolomite and soda avh, may also be changed i.n accordance with the change of these variables.
l0 The following examples at-e to illustrate, but not limit, the scope of the present invention.
The following, is a method for producing an admixture of sodium calcium silicate and sodium magnesium silicate. The reaction takes rlac;e in a paddle mixer. A magnesium oxide and ealciuzn oxide source consisting of 37.? grams dolomitic lime (55.1% CaO; 42.5% Mg0) and 13.2 grams high calcium lime (96%
active) arc pretnixcd in the mixer. To the mixing oxides is added 21U grams of dry sodium mctasilicate pentahydrate. 'this provides enough silicon dioxide to react with all the ma~esium and calcium oxide izt a 1:1 ratio. Into tlxis dry mix is introduced 50 2U grams water. The slurry is allowed to mix for 30 minutes. Upon completion of the r~clion the free water is removed in a kiln at 110°C. The dried material is then heated l0 40U°C'. in a kiln. The phases formed in dais reaction were conErmed by x-ray defraction (X1ZD) to be NaiMgSiU4 and Na~Ca.,Si,O~.
The method wherein a Na~MgSiO,, and Na~CaiSiZO, precursor is used in glass. The glass formulation followed is 74.1% SiO~, 13.3°/u NazU, 8.6%
CaO, and 4.1 % MgU. The precursor material consists of 100% of the needed Na~O, Ca0 and MgO, and 21% of the required SiO~. Therefore, to SU grams precursor material is added 67.9 grams Si()z as sand. A control consistirtd of the above mentioned glass 30 fvt~nulation using calcium carbonate as the Ca0 source, magnesium carbonate as Mg0 source, arid soda ash as the Na~U sou.rcc was created. Two groups of these mixtures rxrere then heated to 1300°C. and 1400°C., respectively, for tunes of 1, 3, 6, and 12 hours. The glass samples Were ground up and XItD performed on them. The %
amorphous glass for these samples were as follows:
1300°C. 1400°C.
,x erizncntal C 1 Ex erimenta.l Contr4l 1 hour 90 80 98 85 3 hours* 98 90 98 85 6 hours -- - 98 95 12 hours -- '-*'rhe control pcrcet~tage is greater at the lower temperature at this time and temperature due to cristobalite formation dynamics.
BXAMPZ.E 3 The following is a method foT synthesizitrg a calcium silicate hydrate.
The reaction takes place in a paddle mixer. 300 grams dolomitic lirn~e consisting 01 55.1% Ca0 and 42.5% Mg0 is slaked with 500 grams water for 10 minutes in the paddle mixer. Separately, 100 grams of b.igh calcium line is slaked with 500 grams water for 10 minutes. Both sa~~nples are screened through a 60 mesh screen.
Tnto the mnixer is placed 400 ml ol' the dolomitic slake and 500 ml of the high calcium slake.
To the mixing slakes is added 945 grams liquid N-type sodium silicate. 'fhe sodium ?0 silicate is introduced over 5 seconds. The sodium silicate provides enough soluble silica to react in a 1:1 molaz ratio with all the Mg0 and CaO. The slurry is allowed to mix for 60 minutes. Upon completion of the reaction the ~zee water is removed in, a kiln at 110°C. The dried material is then heated l0 400°C. in a kiln. The phase fbrmed in this reaction was confirmed by X1ZT7 to be (Ca0),.sSiU~~1~120 along;
with unreacted Mg0 and excess sodium silicate.
EXAMP1~E 4 The method wherein a (CaO)~.5Si02 Hi0 precursor is used in glass. The glass foa-rnulation lollowed is 74.1% SiOZ, 13.3% Na20, 8.6% CaO, and 4.1%
MgO.
'The precursor material consists of 100% of the needed Ca0 and Mt;O. 21% of the 30 required Si02, and 35% of the required NazO. 'therefore, to 20 grams precursor material is added 36.1 grams SiOZ and 9 grams soda ash. A control consisting of the above-mentioned glass formulation using calcium carbonate as the GaU source, lU -magnesiuna carbonate as the MgQ soLtrce, and soda ash as the NazO source was created.
Two groups of these zniatures Werc then heated to 1300°C. atad 1400°C., rcspecti~ely, For times of 1, 3, 6 and 12 hours. The glass samples were. grounded up arad XRD
pet~faraned on them. Tlae % amorphous glass for these: samples were as follows:
1300°C. 1400°C.
Exncrimcnta.l Gotrtrol Bxnerimeatal Gontro_i 1 hour 95 80 98 85 3 hours* 98 9U 99 85 6 hours -- -- 99 95 a0 12 hoots -. __ 99 '~y *The control percentage is greater at the lower temperature at this tizrne and temperature due to cristobalite formation dynamics.
'fhe calcium sylieatc precursor material c;an be further tzeated by heating at higher, temperatures, such as from about 110°C. to about 1100°C., mura preferably lU from about 150°C. to about 700°C., even more preferably below about 300°C. The time and tamping of such healing can be varied, depending upon the desired final calcium silicate precuru~r material inasmuch as such heating can produce fuuhez oz continued reactions.
The calcium silicate precursor material produced by the present invention can have a wide variety of one or more calcium silicate components. 'fhe Variability of calcium silicate components correlates with the variability of amounts of the source of calcium, water and tlae soluble silicate, as well as the conditions of operating, e.g., temperatures, pressures, lime, mixing, ere. 'fhe preferzed calcium silicate components have the formula NaACaB(U)~~UH)"Si~,O~:~G1v20 whezein either C or 1J is zero and the 20 othez subscripted letters vary according to conditions a.~ previously described. Table T
discloses, in a non-limiting way, the pos57ble correlations attainable between operating amounts and calcium silicate precursor material attainable.
Weight Ratios Lime ~ Water ~ Soluble Silica ~ Product 1 1 I 0.5 Cas(OH)ZSibO,~4I~h0 1 1 0.7 C'.aS(OIr)~Si~O,~4H2U
1 3.3 1.7 Ca.,(UI~)ZSi~0,64H.,0 :
1 3.3 0.7 (Ca0),.sSiUiH,O
1 3.3 1.2 (Ca0),,5Si().,HZO
1 7 1.1 Ca0Si02 )<1z0 in a preferred embodiment, the calcium silicate precursor material coanprises one or more components represented by the formula (Ca0)~~SiOZ~Y
(HZO), wherein x is from 5/6 to 3/2 and Y is no zero. Mnre preferably ~c is I .5 and Y is 1.
In another preferred embodiment, the calcium silicate precursor material comprises one or more components represented by the formula X(NazO)~Y(CaU)~Si02 and optionally comprises a compouxad represented by the formula W(NazO)~V(Mp0)~SiO.,, wherein X and W independently arc from l/G to 1/1 and W
and V independently are from 113 to 1/l. Preferably, the; calcium silicate precursor material comprises 0.5(NaZU)~1(Ca0)~Si02. More preferably, the calcium silicate precursor material further comprises Naz,O~Mgt)~SiO,.
In another aspect, the present invention is the setting of process variables within a set of novel process ~ariabtes to attain desired results.
Accordingly, the present ia~,venticm can be the above-described invention wherein the proportion of the amount of calcium silicate precursor material and the amount oJf' tlxe source of silica is effccti~cly controlled to reduce the temperature required to pruduce the molten glass within a set time. l~lternatively, tlae propurtiun eU' the amount of calciuat~
silicate precursor rn.atezial and the amount of the source of silica is effectively controlled to reduce the time required to produce the moltcr~ glass at a set temperature.
'~'be _g_ variables which compose the foregoing variables can also be controlled. 1~or instance, the molten glasa is produced by setting variables from the set of variables consisfiing of the ~atn,ount of slaked Source of calcium,, the amount of soluble silicate, the amount of free water, the amount of the source of silica, tlae time to produce the molten glass, and the temperature to produce the molten glass. Once a certain number of the variables hare been set, the remaining are fixed in accordance with the degree of freedom.
Depending upon the glass composition desired, the amounts cal' other sources of calcium, magnesiutm yr sodium, such as limestone, dolomite and soda avh, may also be changed i.n accordance with the change of these variables.
l0 The following examples at-e to illustrate, but not limit, the scope of the present invention.
The following, is a method for producing an admixture of sodium calcium silicate and sodium magnesium silicate. The reaction takes rlac;e in a paddle mixer. A magnesium oxide and ealciuzn oxide source consisting of 37.? grams dolomitic lime (55.1% CaO; 42.5% Mg0) and 13.2 grams high calcium lime (96%
active) arc pretnixcd in the mixer. To the mixing oxides is added 21U grams of dry sodium mctasilicate pentahydrate. 'this provides enough silicon dioxide to react with all the ma~esium and calcium oxide izt a 1:1 ratio. Into tlxis dry mix is introduced 50 2U grams water. The slurry is allowed to mix for 30 minutes. Upon completion of the r~clion the free water is removed in a kiln at 110°C. The dried material is then heated l0 40U°C'. in a kiln. The phases formed in dais reaction were conErmed by x-ray defraction (X1ZD) to be NaiMgSiU4 and Na~Ca.,Si,O~.
The method wherein a Na~MgSiO,, and Na~CaiSiZO, precursor is used in glass. The glass formulation followed is 74.1% SiO~, 13.3°/u NazU, 8.6%
CaO, and 4.1 % MgU. The precursor material consists of 100% of the needed Na~O, Ca0 and MgO, and 21% of the required SiO~. Therefore, to SU grams precursor material is added 67.9 grams Si()z as sand. A control consistirtd of the above mentioned glass 30 fvt~nulation using calcium carbonate as the Ca0 source, magnesium carbonate as Mg0 source, arid soda ash as the Na~U sou.rcc was created. Two groups of these mixtures rxrere then heated to 1300°C. and 1400°C., respectively, for tunes of 1, 3, 6, and 12 hours. The glass samples Were ground up and XItD performed on them. The %
amorphous glass for these samples were as follows:
1300°C. 1400°C.
,x erizncntal C 1 Ex erimenta.l Contr4l 1 hour 90 80 98 85 3 hours* 98 90 98 85 6 hours -- - 98 95 12 hours -- '-*'rhe control pcrcet~tage is greater at the lower temperature at this time and temperature due to cristobalite formation dynamics.
BXAMPZ.E 3 The following is a method foT synthesizitrg a calcium silicate hydrate.
The reaction takes place in a paddle mixer. 300 grams dolomitic lirn~e consisting 01 55.1% Ca0 and 42.5% Mg0 is slaked with 500 grams water for 10 minutes in the paddle mixer. Separately, 100 grams of b.igh calcium line is slaked with 500 grams water for 10 minutes. Both sa~~nples are screened through a 60 mesh screen.
Tnto the mnixer is placed 400 ml ol' the dolomitic slake and 500 ml of the high calcium slake.
To the mixing slakes is added 945 grams liquid N-type sodium silicate. 'fhe sodium ?0 silicate is introduced over 5 seconds. The sodium silicate provides enough soluble silica to react in a 1:1 molaz ratio with all the Mg0 and CaO. The slurry is allowed to mix for 60 minutes. Upon completion of the reaction the ~zee water is removed in, a kiln at 110°C. The dried material is then heated l0 400°C. in a kiln. The phase fbrmed in this reaction was confirmed by X1ZT7 to be (Ca0),.sSiU~~1~120 along;
with unreacted Mg0 and excess sodium silicate.
EXAMP1~E 4 The method wherein a (CaO)~.5Si02 Hi0 precursor is used in glass. The glass foa-rnulation lollowed is 74.1% SiOZ, 13.3% Na20, 8.6% CaO, and 4.1%
MgO.
'The precursor material consists of 100% of the needed Ca0 and Mt;O. 21% of the 30 required Si02, and 35% of the required NazO. 'therefore, to 20 grams precursor material is added 36.1 grams SiOZ and 9 grams soda ash. A control consisting of the above-mentioned glass formulation using calcium carbonate as the GaU source, lU -magnesiuna carbonate as the MgQ soLtrce, and soda ash as the NazO source was created.
Two groups of these zniatures Werc then heated to 1300°C. atad 1400°C., rcspecti~ely, For times of 1, 3, 6 and 12 hours. The glass samples were. grounded up arad XRD
pet~faraned on them. Tlae % amorphous glass for these: samples were as follows:
1300°C. 1400°C.
Exncrimcnta.l Gotrtrol Bxnerimeatal Gontro_i 1 hour 95 80 98 85 3 hours* 98 9U 99 85 6 hours -- -- 99 95 a0 12 hoots -. __ 99 '~y *The control percentage is greater at the lower temperature at this tizrne and temperature due to cristobalite formation dynamics.
Claims (12)
1. A method of producing a molten glass comprising (1) the step of admixing a slaked source of calcium and a soluble silicate to produce a calcium silicate precursor material, optionally containing free water, and (2) the step of admixing said calcium silicate precursor material and a source of silica to produce a molten glass product.
2. The method of claim 1, wherein the source of calcium is at least one substance selected from the group consisting of dolomite, dolomitic lime, and high calcium lime.
3. The method of claim 1, wherein the source of calcium is dolomitic lime and high calcium lime.
4. The method of claim 2 or 3, wherein the slaked source of calcium is an admixture of separately slaked sources of calcium.
5. The method of any one of claims 1 to 4, wherein the soluble silicate is a sodium silicate.
6. The method of claim 5, wherein the sodium silicate is an anhydrous or hydrated form of a compound having the empirical formula of Na2O.cndot.X SiO2, wherein X ranges in value from 0.5 to 3.75.
7. The method of claim 6, wherein the sodium silicate is Na2O.cndot.SiO2, Na2O.cndot.SiO2.cndot.5H2O, or Na2O.cndot.10/3SiO2.
12 The method of any one of claims 1 to 7, wherein the soluble silicate is admixed after completion of the slaking of the slaked source of calcium.
9. The method of any one of claims 1 to 8, further comprising the step of removing at least a portion of the free water when present in the calcium silicate precursor material.
10. The method of any one of claims 1 to 9, further comprising the step of treating said calcium silicate precursor material at a temperature ranging from about 150°C to about 700°C.
11. The method of any one of claims 1 to 10, wherein the calcium silicate precursor material comprises one or more compounds represented by the formula (CaO)x.cndot.SiO2.cndot.Y(H2O) wherein X is from 5/6 to 3/2 and Y is not zero, or of the formula X(Na2O).cndot.Y(CaO).cndot.SiO2, and optionally comprises a compound represented by the formula W(Na2O).cndot.V(MgO).cndot.SiO2, wherein X and W independently are from 1/6 to 1/1 and Y and V independently are from 1/3 to 1/1.
12. A method of producing molten glass wherein a calcium silicate precursor material comprising one or more compounds represented by the formula (CaO)x.cndot.SiO2.cndot.Y(H2O) wherein X is from 5/6 and 3/2 and Y is not zero, or of the formula X(NaO).cndot.Y(CaO).cndot.SiO2, and optionally comprising a compound represented by the formula W(Na2O).cndot.V(MgO).cndot.SiO2, wherein X and W independently are from 1/6 to 1/1 and Y and V independently are from 1 /3 to 1 /1, is admixed with a source of silica and are subjected to conditions whereby molten glass is produced.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70824696A | 1996-09-03 | 1996-09-03 | |
| US08/708,246 | 1996-09-03 |
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| CA2214363A1 CA2214363A1 (en) | 1998-03-03 |
| CA2214363C true CA2214363C (en) | 2005-11-08 |
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|---|---|---|---|
| CA002214363A Expired - Fee Related CA2214363C (en) | 1996-09-03 | 1997-09-02 | Method of producing synthetic silicates and use thereof in glass production |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0826630B1 (en) |
| JP (2) | JP3246722B2 (en) |
| KR (1) | KR100351232B1 (en) |
| BR (1) | BR9704592A (en) |
| CA (1) | CA2214363C (en) |
| DE (2) | DE69708789T2 (en) |
| ES (1) | ES2116958T3 (en) |
| IL (1) | IL121641A0 (en) |
| PL (1) | PL188364B1 (en) |
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| US6287378B1 (en) * | 1996-09-03 | 2001-09-11 | Minerals Technologies, Inc. | Method of producing synthetic silicates and use thereof in glass production |
| US6211103B1 (en) | 1999-10-12 | 2001-04-03 | Minerals Technologies Inc. | Synthetic silicate pellet compositions |
| US6420289B1 (en) | 1999-10-12 | 2002-07-16 | Minerals Technologies Inc. | Synthetic silicate pellet composition and methods of making and using thereof |
| US6569793B2 (en) * | 2001-02-22 | 2003-05-27 | Specialty Minerals (Michigan) Inc. | Fluidized reaction of synthetic silicates |
| AU2002234091A1 (en) * | 2001-12-27 | 2003-07-24 | Specialty Minerals (Michigan) Inc. | Method of manufacturing glass and compositions therefore |
| BRPI0712438A2 (en) * | 2006-06-01 | 2012-05-29 | Agc Flat Glass Europe Sa | lime glass group composition |
| US20070287624A1 (en) * | 2006-06-13 | 2007-12-13 | Jon Frederick Bauer | Method for preparing glass |
| JP5972050B2 (en) * | 2012-05-25 | 2016-08-17 | 太平洋セメント株式会社 | Method for producing phosphorus recovery material |
| US9890072B2 (en) | 2015-04-01 | 2018-02-13 | Owens-Brockway Glass Container Inc. | Glass precursor gel |
| US10479717B1 (en) | 2016-10-03 | 2019-11-19 | Owens-Brockway Glass Container Inc. | Glass foam |
| US10427970B1 (en) | 2016-10-03 | 2019-10-01 | Owens-Brockway Glass Container Inc. | Glass coatings and methods to deposit same |
| US10364176B1 (en) | 2016-10-03 | 2019-07-30 | Owens-Brockway Glass Container Inc. | Glass precursor gel and methods to treat with microwave energy |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU340257A1 (en) * | 1970-07-06 | 1983-05-07 | Научно-Исследовательский Институт Камня И Силикатов | Method for melting silica glass |
| SU644731A1 (en) * | 1974-05-24 | 1979-01-30 | Институт общей и неорганической химии АН Армянской ССР | Method of obtaining synthetic diopside |
| DD121095A1 (en) * | 1975-04-18 | 1976-07-12 | ||
| DD141015A1 (en) * | 1978-08-17 | 1980-04-09 | Nikolaus Koschwitz | METHOD AND DEVICE FOR INTENSIFYING THE MELTING PROCESS FOR ALKALI ERDALKALI SILICATE GLASS |
| DD141512A1 (en) * | 1979-02-02 | 1980-05-07 | Nikolaus Koschwitz | METHOD FOR PRODUCING SILICATED COMPLEX THREUTS |
| SU823285A1 (en) * | 1979-03-07 | 1981-04-23 | Ереванский Отдел Неорганическихматериалов Всесоюзного Ордена Трудовогокрасного Знамени Научно-Исследовательскогоинститута Химических Реактивови Особо Чистых Химических Веществ | Method of producing sodium-calcium silicate |
| JPS55149122A (en) * | 1979-05-09 | 1980-11-20 | Tokuyama Soda Co Ltd | Manufacture of calcium sodium silicate hydrate |
| SU981217A1 (en) * | 1980-07-23 | 1982-12-15 | Институт общей и неорганической химии АН АрмССР | Process for preparing silica-calcium product |
| DD159987A1 (en) * | 1981-06-26 | 1983-04-20 | Dietmar Petzold | METHOD FOR PRODUCING IMPROVED GLASS HYBRID MATERIAL |
| GB8728892D0 (en) * | 1987-12-10 | 1988-01-27 | Pilkington Plc | Producing molten glass |
-
1997
- 1997-08-27 IL IL12164197A patent/IL121641A0/en unknown
- 1997-09-02 CA CA002214363A patent/CA2214363C/en not_active Expired - Fee Related
- 1997-09-02 KR KR1019970045575A patent/KR100351232B1/en not_active IP Right Cessation
- 1997-09-02 DE DE69708789T patent/DE69708789T2/en not_active Expired - Lifetime
- 1997-09-02 ES ES97306754T patent/ES2116958T3/en not_active Expired - Lifetime
- 1997-09-02 EP EP97306754A patent/EP0826630B1/en not_active Expired - Lifetime
- 1997-09-02 DE DE0826630T patent/DE826630T1/en active Pending
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- 1997-09-03 JP JP23816497A patent/JP3246722B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2116958T3 (en) | 2002-05-16 |
| DE69708789T2 (en) | 2002-07-04 |
| KR19980024286A (en) | 1998-07-06 |
| EP0826630A2 (en) | 1998-03-04 |
| BR9704592A (en) | 1998-11-03 |
| DE69708789D1 (en) | 2002-01-17 |
| CA2214363A1 (en) | 1998-03-03 |
| PL321920A1 (en) | 1998-03-16 |
| JP2002128527A (en) | 2002-05-09 |
| PL188364B1 (en) | 2005-01-31 |
| JP3246722B2 (en) | 2002-01-15 |
| MX9706682A (en) | 1998-07-31 |
| KR100351232B1 (en) | 2002-12-16 |
| ES2116958T1 (en) | 1998-08-01 |
| EP0826630B1 (en) | 2001-12-05 |
| EP0826630A3 (en) | 1998-05-06 |
| DE826630T1 (en) | 1998-09-24 |
| JPH10218638A (en) | 1998-08-18 |
| IL121641A0 (en) | 1998-02-08 |
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